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Detection of CH$_3$C$_3$N in Titans Atmosphere

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 Added by Alexander Thelen
 Publication date 2020
  fields Physics
and research's language is English




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Titan harbors a dense, organic-rich atmosphere primarily composed of N$_2$ and CH$_4$, with lesser amounts of hydrocarbons and nitrogen-bearing species. As a result of high sensitivity observations by the Atacama Large Millimeter/submillimeter Array (ALMA) in Band 6 ($sim$230-272 GHz), we obtained the first spectroscopic detection of CH$_3$C$_3$N (methylcyanoacetylene or cyanopropyne) in Titans atmosphere through the observation of seven transitions in the $J = 64rightarrow63$ and $J = 62rightarrow61$ rotational bands. The presence of CH$_3$C$_3$N on Titan was suggested by the Cassini Ion and Neutral Mass Spectrometer detection of its protonated form: C$_4$H$_3$NH$^+$, but the atmospheric abundance of the associated (deprotonated) neutral product is not well constrained due to the lack of appropriate laboratory reaction data. Here, we derive the column density of CH$_3$C$_3$N to be (3.8-5.7)$times10^{12}$ cm$^{-2}$ based on radiative transfer models sensitive to altitudes above 400 km Titans middle atmosphere. When compared with laboratory and photochemical model results, the detection of methylcyanoacetylene provides important constraints for the determination of the associated production pathways (such as those involving CN, CCN, and hydrocarbons), and reaction rate coefficients. These results also further demonstrate the importance of ALMA and (sub)millimeter spectroscopy for future investigations of Titans organic inventory and atmospheric chemistry, as CH$_3$C$_3$N marks the heaviest polar molecule detected spectroscopically in Titans atmosphere to date.



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Previous investigations have employed more than 100 close observations of Titan by the Cassini orbiter to elucidate connections between the production and distribution of Titans vast, organic-rich chemical inventory and its atmospheric dynamics. However, as Titan transitions into northern summer, the lack of incoming data from the Cassini orbiter presents a potential barrier to the continued study of seasonal changes in Titans atmosphere. In our previous work (Thelen et al., 2018), we demonstrated that the Atacama Large Millimeter/submillimeter Array (ALMA) is well suited for measurements of Titans atmosphere in the stratosphere and lower mesosphere (~100-500 km) through the use of spatially resolved (beam sizes <1) flux calibration observations of Titan. Here, we derive vertical abundance profiles of four of Titans trace atmospheric species from the same 3 independent spatial regions across Titans disk during the same epoch (2012 to 2015): HCN, HC$_3$N, C$_3$H$_4$, and CH$_3$CN. We find that Titans minor constituents exhibit large latitudinal variations, with enhanced abundances at high latitudes compared to equatorial measurements; this includes CH$_3$CN, which eluded previous detection by Cassini in the stratosphere, and thus spatially resolved abundance measurements were unattainable. Even over the short 3-year period, vertical profiles and integrated emission maps of these molecules allow us to observe temporal changes in Titans atmospheric circulation during northern spring. Our derived abundance profiles are comparable to contemporary measurements from Cassini infrared observations, and we find additional evidence for subsidence of enriched air onto Titans south pole during this time period. Continued observations of Titan with ALMA beyond the summer solstice will enable further study of how Titans atmospheric composition and dynamics respond to seasonal changes.
We present spectrally and spatially-resolved maps of HNC and HC$_3$N emission from Titans atmosphere, obtained using the Atacama Large Millimeter/submillimeter Array (ALMA) on 2013 November 17. These maps show anisotropic spatial distributions for both molecules, with resolved emission peaks in Titans northern and southern hemispheres. The HC$_3$N maps indicate enhanced concentrations of this molecule over the poles, consistent with previous studies of Titans photochemistry and atmospheric circulation. Differences between the spectrally-integrated flux distributions of HNC and HC$_3$N show that these species are not co-spatial. The observed spectral line shapes are consistent with HNC being concentrated predominantly in the mesosphere and above (at altitudes $zgtrsim 400$ km), whereas HC$_3$N is abundant at a broader range of altitudes ($zapprox70$-600 km). From spatial variations in the HC$_3$N line profile, the locations of the HC$_3$N emission peaks are shown to be variable as a function of altitude. The peaks in the integrated emission from HNC and the line core (upper-atmosphere) component of HC$_3$N (at $zgtrsim300$ km) are found to be asymmetric with respect to Titans polar axis, indicating that the mesosphere may be more longitudinally-variable than previously thought. The spatially-integrated HNC and HC$_3$N spectra are modeled using the NEMESIS planetary atmosphere code and the resulting best-fitting disk-averaged vertical mixing ratio (VMR) profiles are found to be in reasonable agreement with previous measurements for these species. Vertical column densities of the best-fitting gradient models for HNC and HC$_3$N are $1.9times10^{13}$ cm$^{-2}$ and $2.3times10^{14}$ cm$^{-2}$, respectively.
The precursors to larger, biologically-relevant molecules are detected throughout interstellar space, but determining the presence and properties of these molecules during planet formation requires observations of protoplanetary disks at high angular resolution and sensitivity. Here we present 0.3 observations of HC$_3$N, CH$_3$CN, and $c$-C$_3$H$_2$ in five protoplanetary disks observed as part of the Molecules with ALMA at Planet-forming Scales (MAPS) Large Program. We robustly detect all molecules in four of the disks (GM Aur, AS 209, HD 163296 and MWC 480) with tentative detections of $c$-C$_3$H$_2$ and CH$_3$CN in IM Lup. We observe a range of morphologies -- central peaks, single or double rings -- with no clear correlation in morphology between molecule nor disk. Emission is generally compact and on scales comparable with the millimetre dust continuum. We perform both disk-integrated and radially-resolved rotational diagram analysis to derive column densities and rotational temperatures. The latter reveals 5-10 times more column density in the inner 50-100 au of the disks when compared with the disk-integrated analysis. We demonstrate that CH$_3$CN originates from lower relative heights in the disks when compared with HC$_3$N, in some cases directly tracing the disk midplane. Finally, we find good agreement between the ratio of small to large nitriles in the outer disks and comets. Our results indicate that the protoplanetary disks studied here are host to significant reservoirs of large organic molecules, and that this planet- and comet-building material can be chemically similar to that in our own Solar System. This paper is part of the MAPS special issue of the Astrophysical Journal Supplement Series.
We present the first maps of cyanoacetylene isotopologues in Titans atmosphere, including H$^{13}$CCCN and HCCC$^{15}$N, detected in the 0.9 mm band using the Atacama Large Millimeter/submillimeter array (ALMA) around the time of Titans (southern winter) solstice in May 2017. The first high-resolution map of HC$_3$N in its $v_7=1$ vibrationally excited state is also presented, revealing a unique snapshot of the global HC$_3$N distribution, free from the strong optical depth effects that adversely impact the ground-state ($v=0$) map. The HC$_3$N emission is found to be strongly enhanced over Titans south pole (by a factor of 5.7 compared to the north pole), consistent with rapid photochemical loss of HC$_3$N from the summer hemisphere combined with production and transport to the winter pole since the April 2015 ALMA observations. The H$^{13}$CCCN/HCCC$^{15}$N flux ratio is derived at the southern HC$_3$N peak, and implies an HC$_3$N/HCCC$^{15}$N ratio of $67pm14$. This represents a significant enrichment in $^{15}$N compared with Titans main molecular nitrogen reservoir, which has a $^{14}$N/$^{15}$N ratio of 167, and confirms the importance of photochemistry in determining the nitrogen isotopic ratio in Titans organic inventory.
We report the first detection in space of the single deuterated isotopologue of methylcyanoacetylene, CH$_2$DC$_3$N. A total of fifteen rotational transitions, with $J$ = 8-12 and $K_a$ = 0 and 1, were identified for this species in TMC-1 in the 31.0-50.4 GHz range using the Yebes 40m radio telescope. The observed frequencies were used to derive for the first time the spectroscopic parameters of this deuterated isotopologue. We derive a column density of $(8.0pm 0.4) times 10^{10}$ cm$^{-2}$. The abundance ratio between CH$_3$C$_3$N and CH$_2$DC$_3$N is $sim$22. We also theoretically computed the principal spectroscopic constants of $^{13}$C isotopologues of CH$_3$C$_3$N and CH$_3$C$_4$H and those of the deuterated isotopologues of CH$_3$C$_4$H for which we could expect a similar degree of deuteration enhancement. However, we have not detected either CH$_2$DC$_4$H nor CH$_3$C$_4$D nor any $^{13}$C isotopologue. The different observed deuterium ratios in TMC-1 are reasonably accounted for by a gas phase chemical model where the low temperature conditions favor deuteron transfer through reactions with H$_2$D$^+$.
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